Tannin-Based Copolymer Resins: Synthesis and Characterization by Solid State 13C NMR and FT-IR Spectroscopy

In recent years, the interest for bio-sources is rising exponentially and tannins extracts are one of the most interesting, easily-available, phenolic building blocks. The condensed tannins or proanthocyanidins are already known for their polymerization chemistry, which is the basis for several natural-based materials (e.g., adhesives, foams). In the present work we aim to observe the behavior of the extract of Acacia Mimosa (Acacia mearnsii) when reacted with several possible co-monomers at different relative amount, pH and temperature conditions. The more insoluble copolymers obtained with formaldehyde, hexamine, glyoxal, maleic anhydride, furfural and furfuryl alcohol were analyzed through solid state 13C NMR (Nuclear magnetic resonance) and FT-IR (Fourier Transform-Infrared) spectroscopy. The 13C NMR afforded the opportunity to detect: (i) aromatic substitutions and consequent poly-condensations for the majority of the hardeners studied; (ii) acylation for the maleic anhydride and also some; (iii) Diels–Alder arrangements for the furanic co-monomers; the FT-IR spectroscopy suggested that the formaldehyde and hexamine copolymers present a higher cross-linking degree.